CN102505548B - Synchronous remover for mixed impurities of ink and adhesive in waste paper, and preparation method thereof - Google Patents
Synchronous remover for mixed impurities of ink and adhesive in waste paper, and preparation method thereof Download PDFInfo
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- CN102505548B CN102505548B CN2011103484493A CN201110348449A CN102505548B CN 102505548 B CN102505548 B CN 102505548B CN 2011103484493 A CN2011103484493 A CN 2011103484493A CN 201110348449 A CN201110348449 A CN 201110348449A CN 102505548 B CN102505548 B CN 102505548B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention provides a synchronous remover for mixed impurities of ink and adhesive in waste paper, and preparation method thereof. The preparation method comprises the steps of: firstly, ultra-filtering lignin raw materials or pulping waste liquor and classifying, taking components of which molecular weights are in a range from 3, 000 to 5, 000; and then carrying out hydroxymethylation modification to the components and formaldehyde in alkaline condition, obtaining modified lignin product; roasting inorganic mineral clay, and then modifying the inorganic mineral clay by using alkylammonium, obtaining modified organic mineral clay; and compounding 12%-20% of the modified lignin product, 15-%-20% of ink capturing agent, 8%-12% of penetrating agent or emulsifying agent, 1%-5% of foam stabilizer, and the balance of the modified organic mineral clay according to a formula, thereby obtaining the synchronous remover (wherein the percentages are all mass percentages). The preparation method disclosed by the invention is simple; the synchronous remover obtained by the preparation method has excellent effects to increase of whiteness in secondary fiber pulping and flotation and to removal of the ink and the adhesive.
Description
Technical field
The present invention relates to the removal of printing ink in waste paper pulp-making, sicker, be specifically related to a kind of waste paper printing ink and the synchronous remover of sicker poly-doped impurity and preparation method thereof.
Background technology
Secondary stock is one of important paper making raw material, and the reuse of waste paper is to solve the effective way that paper industry faces the problems such as there is lack of raw materials, seriously polluted.Utilize waste paper to produce recycled writing paper and have the plurality of advantages such as low in the pollution of the environment, that technological process is simple, energy consumption is low, have good economic and social benefit.
Waste paper is compared with original plant fiber material as paper making raw material, does not generally contain pectin, resin, solvent extractable matter, ash grade plant material and natural intrinsic organic matter and inorganic matter impurity.The main component that forms waste paper is cellulose and hemicellulose, is secondly owing to processing and using the foreign material of bringing into.These foreign material are varied, comprise printing ink, wax class, resin impregnator, plastic sheeting, metallic film, synthetic resin, hot-melt object, adhesive, various inorganic filler, coating and bookbinding staple, greasy dirt, silt etc.Although the composition more complicated of waste paper, but easy to be easy to be more than using primordial plant fiber pulping and paper-making, regenerated fiber slurrying not only production procedure is simplified, and greatly saves equipment investment, but also can save electric power, fuel and chemicals, production cost is greatly descended; But the various foreign material in waste paper are extremely harmful to pulping and paper-making, permitted polymictic removal and be not easy again, so the high-efficiency cleaning reuse of waste paper is faced with a lot of problems.Wherein, the impact especially brought with printing ink and sicker is the most outstanding.
At present, although the development of deinking technology and equipment is comparatively ripe, but the ink formulations that press is used and printing technology but, in development, also make thus the deinking technology can not defend tenaciously existing technology, and must constantly develop thereupon and improve.In addition, the sicker in waste paper also is on the rise for paper-making industry harm, towards the modernization mode development of energy-saving and emission-reduction, brings adverse effect for paper industry.Therefore, in the face of the problem constantly occurred in these production practices, must continue further investigation to deinking technology and stickies removal problem.
In the situation that current wastepaper as raw material quality constantly worsens, still deinking and two problems of gluing thing are studied respectively to the needs that can not meet production practices, only have and treat this problem comprehensively, the comprehensive removal effect of research impurity, just have more realistic meaning.
Summary of the invention
For improving the waste paper flotation effect, reduce simultaneously printing ink and adhesive content, the invention provides synchronous remover of waste paper printing ink and sicker poly-doped impurity and preparation method thereof.
The preparation of the synchronous remover of useless waste paper printing ink and sicker poly-doped impurity is achieved by the following technical programs:
(1) lignin raw material or pulping waste liquor being adjusted to mass concentration is to carry out classification after 10%～15% solution, gets the part between molecular weight 3000～5000, concentrates, the dry processing lignin raw material that obtains making with extra care;
(2) the lignin raw material that will make with extra care adds formalin after with NaOH solution, dissolving, and carries out hydroxymethylation 2h～5h under 40 ℃～80 ℃ conditions; NaOH solution is 6ml/g～10ml/g with the volume mass ratio of the lignin raw material made from extra care; Formaldehyde is 10ml/g～15ml/g with the volume mass ratio of the lignin raw material made from extra care;
(3) pH of the reactant liquor of adjusting after step (2) is processed<3, be precipitated, or the reactant liquor after step (2) is processed is concentrated, then dry; Gained precipitation or dry rear solid are lignin modified product; Regulate pH and adopt watery hydrochloric acid or dilute sulfuric acid;
(4) the mineral clay original soil is carried out to high-temperature calcination, obtain calcining mineral clay; Then it is mixed with alkylammonium solution, process 12h～48h, the then resulting product of centrifugal ultrasonic processing through ultrasonic wave, remove supernatant liquid, wash remaining solid with water 3 times～5 times, then by solid drying and grind, cross 200 orders～400 mesh sieves, obtain organically-modified mineral clay;
(5) by lignin modified product 12%～20%, trapping ink agent 15%～20%, bleeding agent or emulsifying agent 8%～12%, foam stabilizer 1%～5%, surplus is that the organic modified mineral clay mixes, and is combined into synchronous remover; Above percentage is mass percent.
Perhaps first by step (4), prepare organically-modified mineral clay, then prepare lignin modified product by step (1) to (3) is described, and then composite by step (5), be mixed to get synchronous remover.
Described alkylammonium is that carbon number is 12～18 alkyl ammonium halide, and its consumption is 0.01 times～0.05 times of calcining mineral clayey amount; Ultrasonic wave is processed 40 ℃～80 ℃ of frequency 80KHz～100KHz, temperature.
The LCFA salt that described trapping ink agent is carbon number 12～18.
As preferably, described LCFA salt is the sodium salt of laurate, myristic acid, palmitic acid, stearic acid, oleic acid or more than one in sylvite.
Described bleeding agent is the fatty alcohol polyethenoxy ether class material, as AEO-9; Emulsifying agent is alkylphenol polyoxyethylene class material, as OP-10.
Described foam stabilizer is anion surfactant or non-ionic surface active agent.
As preferably, described anion surfactant is lauryl sodium sulfate or α-sodium olefin sulfonate; Non-ionic surface active agent is that carbon number is 12～18 direct-connected alkylolamides or DDAO.
It is diatomite, bentonite or palygorskite that described humatite clay prepares raw material used.
For further realizing goal of the invention, the temperature of described temperature calcining is 200 ℃～500 ℃, and calcination time is 0.5h～2.5h
By the synchronous remover of the preparation-obtained printing ink of above-mentioned preparation method and sicker poly-doped impurity, after it was applied to the secondary stock deinking, its brightness gain was near 70%, and the sicker clearance is also more than 55%.
Compared with prior art, the present invention has the following advantages:
1, the prepared synchronous remover of the present invention can be removed printing ink, sicker poly-doped impurity efficiently in floatation process, can enhance productivity, and reduces the energy consumption of follow-up workshop section;
2, the present invention provides a concrete application direction for the lignin higher value application, can also create certain economic benefit simultaneously;
3, the inventive method technique is simple, is easy to preparation.
The specific embodiment
Below in conjunction with some concrete application examples, the present invention is done to further detailed description.These examples only are not used in and limit the scope of the invention be used to the present invention is described.Other are any does not deviate from change, the modification done under Spirit Essence of the present invention and principle, substitute, in conjunction with, simplify, be equivalents, belong to equally the application's appended claims limited range.
Embodiment 1
(1) alkaline pulp black liquor being mixed with to mass fraction is 10% solution, with ultrafilter, lignin raw material in solution is carried out to classification, gets the part between molecular weight 3000～5000, concentrates, the dry processing lignin raw material that obtains making with extra care;
(2) get refining lignin raw material 100g, add the NaOH solution of 600ml10% and the formalin of 1500ml37%, then add water to 2500ml, react 2h under 80 ℃ of conditions; After completion of the reaction, the watery hydrochloric acid with 10% is regulated pH<3, and the product Precipitation is centrifugal, removes supernatant liquor, and the water washing of precipitation use pH=2 3 times, 35 ℃ of lower vacuumizes, obtain lignin modified product afterwards;
(3) diatomite original soil is calcined to 0.5h under 500 ℃ of conditions, obtain calcined diatomite;
(4) in reactor, add again 400ml water, get the 100g calcined diatomite and put into reactor, separately get the 1g DTAB water-soluble solution of 100ml, also add in reactor, afterwards reactor is put into to supersonic generator, ultrasonic wave is processed 12h under frequency 80KHz, 80 ℃ of conditions of temperature;
(5) after ultrasonic wave is finished dealing with, product is centrifugal, removal supernatant liquid, wash solid with water 3 times, and solid is air-dry, grinds rear mistake 300 mesh sieves, obtains organically-modified diatomite;
(6) get respectively 10g potassium stearate, palmitic acid potassium 10g, the lignin modified product of 12g, 8g bleeding agent AEO-9,1g lauryl sodium sulfate and the organically-modified diatomite of 59g, join in reactor, stir, this remover numbering 1#.
Embodiment 2
(1) the acid sulfite process waste liquid being modulated into to mass fraction is 12% solution, with ultrafilter, lignin raw material in solution is carried out to classification, gets the part between molecular weight 3000～5000, concentrates, the dry processing lignin raw material that obtains making with extra care;
(2) get refining lignin raw material 100g, add the NaOH solution of 1000ml10% and the formalin of 1500ml37%, then add water to 3000ml, react 5h under 40 ℃ of conditions; After completion of the reaction, the ultrafiltration concentration reactant liquor, then, 45 ℃ of lower vacuumizes, obtain lignin modified product;
(3) the bentonite original soil is calcined to 1.5h under 300 ℃ of conditions, obtain calcining bentonite;
(4) in reactor, add again 400ml water, get the 100g calcined diatomite and put into reactor, separately get the 5g hexadecyltrimethylammonium chloride water-soluble solution of 100ml, also add in reactor, afterwards reactor is put into to supersonic generator, under frequency 80KHz, temperature 60 C condition, ultrasonic wave is processed 48h;
(5) after ultrasonic wave is finished dealing with, product is centrifugal, removal supernatant liquid, wash solid with water 5 times, and solid is dried, and grinds rear mistake 300 mesh sieves, obtains organically-modified bentonite;
(6) get respectively 15g laurate acid sodium, the lignin modified product of 20g, 12g emulsifier op-10,1g α-sodium olefin sulfonate and the organically-modified bentonite of 52g, join in reactor, stir, this remover numbering 2#.
Embodiment 3
(1) lignosulphonates being mixed with to mass fraction is 10% solution, with ultrafilter, lignin raw material in solution is carried out to classification, gets the part between molecular weight 3000～5000, concentrates, the dry processing lignin raw material that obtains making with extra care;
(2) get refining lignin raw material 200g, add the NaOH solution of 1200ml10% and the formalin of 2000ml37%, then add water to 3500ml, react 3h under 60 ℃ of conditions; After completion of the reaction, the reactant liquor rotary evaporation is concentrated, then, 50 ℃ of lower vacuumizes, obtain lignin modified product;
(3) the palygorskite original soil is calcined to 1h under 400 ℃ of conditions, obtain calcining palygorskite;
(4) in reactor, add again 400ml water, get the 100g calcined diatomite and put into reactor, separately get the 3g Tetradecyl Trimethyl Ammonium Bromide water-soluble solution of 100ml, also add in reactor, afterwards reactor is put into to supersonic generator, ultrasonic wave is processed 24h under frequency 100KHz, temperature 50 C condition;
(5) after ultrasonic wave is finished dealing with, product is centrifugal, removal supernatant liquid, wash solid with water 4 times, and solid is dried, and grinds rear mistake 300 mesh sieves, obtains organically-modified palygorskite;
(6) get respectively 15g potassium stearate, 5g sodium laurate, the lignin modified product of 20g, 10g bleeding agent AEO-9,3g DDAO and the organically-modified palygorskite of 47g, join in reactor, stir, this remover numbering 3#.
Embodiment 4
(1) alkali lignin being mixed with to mass fraction is 10% solution, with ultrafilter, lignin raw material in solution is carried out to classification, gets the part between molecular weight 3000～5000, concentrates, the dry processing lignin raw material that obtains making with extra care;
(2) get refining lignin raw material 100g, add the NaOH solution of 800ml10% and the formalin of 1500ml37%, then add water to 1000ml, react 4h under 50 ℃ of conditions; After completion of the reaction, the watery hydrochloric acid with 10% is regulated pH<3, and the product Precipitation is centrifugal, removes supernatant liquor, and the water washing of precipitation use pH=2 3 times, 30 ℃ of lower vacuumizes, obtain lignin modified product afterwards;
(3) diatomite original soil is calcined to 2.5h under 200 ℃ of conditions, obtain calcined diatomite;
(4) in reactor, add again 400ml water, get the 100g calcined diatomite and put into reactor, separately get the 2g DTAB water-soluble solution of 100ml, also add in reactor, afterwards reactor is put into to supersonic generator, under frequency 80KHz, temperature 70 C condition, ultrasonic wave is processed 36h;
(5) after ultrasonic wave is finished dealing with, product is centrifugal, removal supernatant liquid, wash solid with water 3 times, and solid is air-dry, grinds rear mistake 300 mesh sieves, obtains organically-modified diatomite;
(6) get respectively 12g sodium palmitate, the lignin modified product of 15g, 8g emulsifier op-10,5g lauryl sodium sulfate and the organically-modified diatomite of 60g, join in reactor, stir, this remover numbering 4#.
The application of synchronous remover
The papers for books and periodicals that gives up of take is example, and the synchronous remover prepared to various embodiments of the present invention carries out pulping and float test.
The pulping condition is: pulping slurry is dense 13%, temperature 60 C, time 20min; The chemicals addition is (all for the oven dry stock quality): NaOH0.5%, Na
2SiO
30.3%, H
2O
20.5%, synchronous remover consumption 0.2%, above.Pulper: the U.S. produces FORMAX N-100 type pulper, and the highest pulping concentration is 15%.
Flotation conditions is: starch dense 1%, time 5min, temperature 50 C.Floatation equipment: the German VIOTH product Delta25 of company use for laboratory flotation deinking tank, dischargeable capacity is 23L.
Sicker detects: get the 20g oven dry stock and sieve through pulp classifier, pulp classifier is the Canadian Pulmac manufacture MasterScreen MS-B3 of company type, and sieve seam used is 0.15mm, and software kit is the Spec& of U.S. ApogeeSystems company research and development; Scan, coordinate hewlett-packard scanner to use.Detect respectively broken rear and floating rear adhesive content.
With the slurry that does not add any chemicals and synchronous remover, compare experiment.Whiteness and residual ink are measured on ColorTouch PC type residual ink analyzer.The testing result of whiteness, residual ink and sicker is respectively as shown in table 1, table 2 and table 3.
Table 1
Table 2
Table 3
Result by above application example, whiteness has the raising of highly significant, the printing ink clearance approaches or reaches 70% left and right, simultaneously the removal of sicker is also had to obvious increase, and remover prepared by the present invention all has removal effect preferably to printing ink and sicker.
Claims (10)
1. the preparation method of the synchronous remover of waste paper printing ink and sicker poly-doped impurity is characterized in that step is as follows:
(1) lignin raw material or pulping waste liquor being modulated into to mass concentration is to carry out classification after 10%～15% solution, gets the part between molecular weight 3000～5000, concentrates, the dry processing lignin raw material that obtains making with extra care;
(2) the lignin raw material that will make with extra care adds formalin after with NaOH solution, dissolving, and carries out hydroxymethylation 2h～5h under 40 ℃～80 ℃ conditions; NaOH solution is 6mL/g～10mL/g with the volume mass ratio of the lignin raw material made from extra care; Formaldehyde is 10mL/g～15mL/g with the volume mass ratio of the lignin raw material made from extra care;
(3) pH of the reactant liquor of adjusting after step (2) is processed<3, be precipitated, or the reactant liquor after step (2) is processed is concentrated, then dry; Gained precipitation or dry rear solid are lignin modified product;
(4) the mineral clay original soil is carried out to high-temperature calcination, obtain calcining mineral clay; Then it is mixed with alkylammonium solution, process 12h～48h, the then resulting product of centrifugal ultrasonic processing through ultrasonic wave, remove supernatant liquid, wash remaining solid with water 3 times～5 times, then by solid drying and grind, cross 200 orders～400 mesh sieves, obtain organically-modified mineral clay;
(5) by lignin modified product 12%～20%, trapping ink agent 15%～20%, bleeding agent or emulsifying agent 8%～12%, foam stabilizer 1%～5%, surplus is that the organic modified mineral clay mixes, and is combined into synchronous remover; Above percentage is mass percent;
Perhaps first by step (4), prepare organically-modified mineral clay, then prepare lignin modified product by step (1) to (3) is described, and then composite by step (5), be mixed to get synchronous remover.
2. preparation method according to claim 1, is characterized in that described alkylammonium is that carbon number is 12～18 alkyl ammonium halide, and its consumption is 0.01 times～0.05 times of calcining mineral clayey amount; Ultrasonic wave is processed 40 ℃～80 ℃ of frequency 80KHz～100KHz, temperature.
3. preparation method according to claim 1, is characterized in that the LCFA salt that described trapping ink agent is carbon number 12～18.
4. preparation method according to claim 3, is characterized in that described LCFA salt is the sodium salt of laurate, myristic acid, palmitic acid, stearic acid, oleic acid or more than one in sylvite.
5. preparation method according to claim 1, is characterized in that described bleeding agent is the fatty alcohol polyethenoxy ether class material; Emulsifying agent is alkylphenol polyoxyethylene class material.
6. preparation method according to claim 1, is characterized in that described foam stabilizer is anion surfactant or non-ionic surface active agent.
7. preparation method according to claim 6, is characterized in that described anion surfactant is lauryl sodium sulfate or α-sodium olefin sulfonate; Non-ionic surface active agent is that carbon number is 12～18 straight chained alkyl alkylolamides.
8. preparation method according to claim 1, is characterized in that described mineral clay is diatomite, bentonite or palygorskite.
9. according to the described preparation method of one of claim 1 to 8, the temperature that it is characterized in that described high-temperature calcination is 200 ℃～500 ℃, and calcination time is 0.5 h～2.5h.
10. the synchronous remover of the prepared waste paper printing ink of the described preparation method of one of claim 1 to 9 and sicker poly-doped impurity.
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| CN104312259B (en) * | 2014-10-13 | 2016-09-14 | 濮阳宏业环保新材料股份有限公司 | A kind of deinking bleach and preparation method thereof |
| CN107366174B (en) * | 2017-08-31 | 2019-04-09 | 华南理工大学 | A kind of mthod of white water from paper making microstickies efficiently stick purification method and device |
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